CN104447161A - Ethylene oligomerization method - Google Patents
Ethylene oligomerization method Download PDFInfo
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Abstract
The present invention discloses an ethylene oligomerization method, wherein ethylene is subjected to an oligomerization reaction in a reaction system containing an isobutyryl substituted 1,10-phenanthroline aminal iron (II) complex coordination compound main catalyst represented by a formula (I), an aluminum-containing assisted catalyst, water and a solvent, and the solvent is alpha-olefin of Cn (n is more than 4 and is less than or equal to 10), wherein in the formula (I), R1-R5 are respectively and independently selected from hydrogen, C1-C6 alkyl, halogen, C1-C6 alkoxy and nitro. According to the present invention, the technical prejudice is overcome, the oligomerization process is optimized, the oligomerization activity is high, and advantages of rapid ethylene oligomerization reaction process initiation, stable operation, low toxicity, environmental protection, good catalytic effect and cost balancing, and strong practicality; and the ethylene oligomerization reaction cost is substantially reduced, the catalysis effect and the production cost are comprehensively considered, and the industrialization prospects are broad.
Description
Technical field
The present invention relates to field of olefin polymerisation, be specifically related to a kind of method of ethylene oligomerization.
Background technology
Linear alpha-alkene has a wide range of applications in fields such as ethylene comonomer, synthesis of surfactant intermediate, softening agent alcohol, ucon oil and oil dopes.In recent years, along with the development of polyolefin industry, the demand rapid development to alpha-olefin in world wide.The alpha-olefin of the current overwhelming majority is obtained by ethylene oligomerization preparation.Ethylene oligomerization method catalyzer used mainly contains nickel system, chromium system, zirconium system and aluminium system etc., in recent years, and Brookhart group (people such as Brookhart, M, J.Am.Chem.Soc., 1998,120,7143-7144; WO99/02472,1999), Gibson group (people such as Gibson, V.C., Chem.Commun., 1998,849-850; Chem.Eur.J., 2000,2221-2231) find that the trident pyridinimine title complex of some Fe (II) and Co (II) can catalyzed ethylene oligomerisation respectively, not only the catalytic activity of catalyzer is very high, and the selectivity of alpha-olefin is also very high.
The patent CN102050841A of Institute of Chemistry, Academia Sinica reports a kind of catalyzer for ethylene oligomerization and polymerization, this catalyzer is with 2-propionic acid amide-1,10-phenanthroline anil class title complex is Primary Catalysts, methylaluminoxane or modified methylaluminoxane are promotor, in ethylene oligomerization reaction, have good oligomerisation and polymerization catalyzed performance, wherein iron complex shows very high oligomerisation and polymerization activity to ethene.But when adopting methylaluminoxane or modified methylaluminoxane to be promotor, only when amount ratio higher (Al/Fe=1000 ~ 2000), oligomerization activity just can reach 10
7gmol
-1h
-1.And no matter be methylaluminoxane, or modified methylaluminoxane, unit price is all higher, when on a large scale for ethylene oligomerization, production cost certainly will be caused high.And oligomerisation reaction is very harsh to the environmental requirement caused, and it has been generally acknowledged that water is very disadvantageous to ethylene oligomerization reaction process.As CN200810111717.8 discloses a kind of method of ethylene oligomerization, carry out under being strict controlled in the environment of anhydrous and oxygen-free, cause the reaction initiation of oligomerisation reaction technique and all non-constant of repeatability.In addition, the solvent in oligomerization is all generally toluene, and as everyone knows, toluene is poisonous aromatic hydrocarbon, irritant to skin, mucous membrane, has anesthetic action to central nervous system; And in oligomerization product, toluene level is comparatively large, cannot reach the requirement to aromatic hydrocarbon content when using as comonomer.
Summary of the invention
For the defect of prior art; contriver has carried out research extensively and profoundly in ethylene oligomerization catalyst field; be surprised to find; ethene is comprising 1 of isobutyryl replacement; 10-phenanthroline contracting amine closes iron (II) title complex Primary Catalysts, carries out oligomerisation reaction containing in the reaction system of aluminum cocatalyst and solvent; described solvent is the alpha-olefin of Cn (4 ﹤ n≤10), and oligomerisation reaction activity can reach 10
7gmol
-1h
-1above, the consumption containing aluminum cocatalyst is few, and what this and prior art were approved only have adopts the aikyiaiurnirsoxan beta of large consumption, high cost just to have the idea of high oligomerisation and polymerization activity to have marked difference as promotor; Reaction system is moisture, can obtain higher oligomerisation reaction on the contrary active, overcome prejudice of the prior art, oligomerisation reaction can be made simultaneously to cause rapidly, operate steadily, reproducible.In addition, solvent is changed into Cn (4 ﹤ n≤10) by the toluene in traditional technology) alpha-olefin, not only reduce toxicity, decrease the consumption of chemical reagent, and the aromatic hydrocarbon content in product is reduced greatly.Therefore, in ethylene oligomerization technique, adopt this method can ensure for heavy industrialization provides powerful.
According to the present invention; provide a kind of ethylene oligomerization method; described ethene is comprising 1 of the replacement of the isobutyryl shown in following formula (I); 10-phenanthroline contracting amine closes iron (II) title complex Primary Catalysts, carries out oligomerisation reaction containing in the reaction system of aluminum cocatalyst and solvent, and described solvent is C
nalpha-olefin, wherein n≤10,
In formula, R
1-R
5be selected from hydrogen, C independently of one another
1-C
6alkyl, halogen, C
1-C
6alkoxyl group and nitro.
According to method provided by the invention, containing water in reaction system, but ethylene oligomerization has higher oligomerisation reaction activity on the contrary, and the selectivity of alpha-olefin is high; Abandon the aromatic solvent that toxicity is large, not only environmental protection, and eliminated the step of separating aromatic solvent, simplify production technique.
In the reaction system of the inventive method, with the weight of organic solvent for Calculation Basis, the weight content of water be 5 ~ 350ppm(namely based on the organic solvent of 1g, containing 5 ~ 350 × 10 in reaction system
-6the water of g), preferably 20 ~ 260ppm, most preferably is 50 ~ 200ppm.Within the scope of described water-content, in described method, ethylene oligomerization has higher ethylene oligomerization activity.
In the present invention, term " C
1-C
6alkyl " refer to saturated straight chain containing 1-6 carbon atom or branched hydrocarbyl.As C
1-C
6alkyl, can mention methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, n-hexyl and Sec-Hexyl; Particularly preferably methyl, ethyl, n-propyl and sec.-propyl.
In the present invention, term " C
1-C
6alkoxyl group " refer to above-mentioned C
1-C
6alkyl is connected with a Sauerstoffatom group obtained.As C
1-C
6alkoxyl group, can mention methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, secondary pentyloxy, positive hexyloxy and secondary hexyloxy; Particularly preferably methoxyl group and oxyethyl group.
In the present invention, term " halogen " refers to fluorine, chlorine, bromine and iodine, particularly preferably fluorine, chlorine and bromine.
In the present invention, described " C
nthe alpha-olefin of (n≤10) " refer to containing n carbon atom alpha-olefin, it can be selected from 1-hexene, 1-octene, 1-decene, 2-ethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 2,3-dimethyl-1-hexene, 2,4-dimethyl-1-hexene, 2,5-dimethyl-1-hexene, 3,4-dimethyl-1-hexene, 3,5-dimethyl-1-hexene, 4,5-dimethyl-1-hexene, 3,3-dimethyl-1-hexene, 4,4-dimethyl-1-hexene, 5,5-dimethyl-1-hexene, 2,3-diethyl-1-hexene, 2,4-diethyl-1-hexene, 3,4-diethyl-1-hexene, 3,3-diethyl-1-hexene, 4,4-diethyl-1-hexene, 2-ethyl-1-octene, 3-ethyl-1-octene, 4-ethyl-1-octene, 5-ethyl-1-octene, 6-ethyl-1-octene, 2,3-dimethyl-1-octene, 2,4-dimethyl-1-octene, 2,5-dimethyl-1-octene, 2,6-dimethyl-1-octene, 2,7-dimethyl-1-octene, 3,3-dimethyl-1-octene, 3,4-dimethyl-1-octene, 3,5-dimethyl-1-octene, 3,6-dimethyl-1-octene, 4,4-dimethyl-1-octene, 4,5-dimethyl-1-octene, 4,6-dimethyl-1-octene, 4,7-dimethyl-1-octene, 5,5-dimethyl-1-octene, 5,6-dimethyl-1-octene, 5,7-dimethyl-1-octene, 6,6-dimethyl-1-octene and 6,7-dimethyl-1-octene, be particularly preferably selected from 1-hexene and 1-octene.
In described method of the present invention, the consumption of described Primary Catalysts and promotor can be selected according to the processing condition during embody rule such as industrial scale and production unit.In a specific embodiment of the inventive method, with the volume of organic solvent for Calculation Basis, the content of described Primary Catalysts be 2 ~ 500 μm of ol/L(namely based on the organic solvent of 1L, containing 2 ~ 500 × 10 in reaction system
-6the Primary Catalysts of mol), preferably 20 ~ 100 μm of ol/L.
In the above-mentioned methods, the R in described Primary Catalysts
1-R
5be selected from hydrogen, methyl, ethyl, n-propyl, sec.-propyl, fluorine, chlorine, bromine, methoxyl group, oxyethyl group and nitro independently of one another, preferred R
1and R
5for ethyl, and R
2-R
4be hydrogen.
The preparation method that the ethylene oligomerization Primary Catalysts of general formula of the present invention (I) can adopt Chinese patent application CN102558242A to report obtains.Therefore, the concrete preparation process that 1, the 10-phenanthroline contracting amine that the isobutyryl of general formula (I) replaces closes iron (II) title complex is as follows:
A.2-the synthesis of isobutyryl-1,10-phenanthroline: make 1,10-phenanthroline and triisobutyl aluminium (i-C
4h
9)
3al reacts, more successively through hydrolysis and the oxidizing reaction with oil of mirbane, obtains formula (b) compound.
In order to 2-isobutyryl-1, the 10-phenanthroline of preparation formula (b), first make 1,10-phenanthroline and triisobutyl aluminium (i-C
4h
9)
3al reacts in the presence of an organic.Operable organic solvent is selected from toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene, methylene dichloride or its mixture etc. for this reason, preferred toluene.Utilize these organic solvents, preparation 1,10-phenanthroline solution, wherein strength of solution is 10 ~ 200g/L.The reaction of this 1,10-phenanthroline and triisobutyl aluminium, usually at-60 ~-80 DEG C, is preferably carried out at-60 ~-70 DEG C.In addition, this reaction is advantageously carried out under protection of inert gas, the preferred argon gas of this rare gas element or nitrogen.1,10-phenanthroline can use anhydrous 1,10-phenanthroline, also can use hydration 1,10-phenanthroline, preferably anhydrous 1,10-phenanthroline.Triisobutyl aluminium uses with itself usually.The mol ratio of 1,10-phenanthroline and triisobutyl aluminium is 1:0.5 ~ 1:4.5, preferred 1:2.0 ~ 1:2.6.Advantageously, this reaction adds triisobutyl aluminium usually at the reaction temperatures in 1,10-phenanthroline solution, such as, drip triisobutyl aluminium and carry out.After reinforced, stir 18 ~ 28 hours at the reaction temperatures, preferably 18 ~ 20 hours.Afterwards, reaction mixture is warming up to 20 ~ 40 DEG C and stirs 5 ~ 10 hours again, preferably 10 hours, to react more completely.Then add water (preferred deionized water) be hydrolyzed at-60 ~ 0 DEG C.Such as, reaction mixture is remained-30 DEG C and add water and be hydrolyzed, preferably add deionized water and be hydrolyzed.In hydrolytic process, have bubble to emerge, hydrolysis is until bubble is no longer emerged.In order to more complete hydrolysis, reaction mixture is warming up to 20 ~ 40 DEG C again and stirs 5 ~ 10 hours.Then separatory, takes out organic phase.In order to isolate required product as much as possible, preferably also to inorganic phase organic solvent extraction, the organic phase obtained and the organic phase that separatory obtains before are merged, can be ethyl acetate to this operable organic solvent, acetone, methylene dichloride or its mixture etc., preferred methylene dichloride.After the organic phase removed under reduced pressure solvent of organic phase or merging, add oil of mirbane backflow (such as at 210 DEG C) 10 ~ 48 hours, preferably 15 ~ 24 hours.Filter afterwards, removed under reduced pressure solvent.Ethyl acetate with volume ratio is 1:1 ~ 1:5, preferred 1:2: the mixing solutions of sherwood oil is leacheate, carries out silica gel column chromatography, obtains solid product, be i.e. formula (b) compound.In this synthesis step, the mol ratio of 1,10-phenanthroline and oil of mirbane is 1:0.5 ~ 1:30, preferred 1:15 ~ 1:20.
B.2-the synthesis of isobutyryl-1,10-phenanthroline contracting amine ligand: formula (b) compound and formula (c) compound are reacted under tosic acid exists as catalyzer, obtains formula (d) compound
Wherein R
1-R
5as mutual-through type (I) define.
Product part (d) is by making the 2-isobutyryl-1 obtained in step a in a reservoir; the substituted aniline of 10-phenanthroline and formula (c); reaction in the organic solvent of not moisture and oxygen and preparing; wherein the mol ratio of the substituted aniline of 2-isobutyryl-1,10-phenanthroline and formula (c) is 1:1 ~ 1:5.Toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene, methylene dichloride or its mixture etc. are selected to this operable organic solvent, preferred toluene.This reaction is carried out for catalyzer under reflux with tosic acid (p-TsOH), such as, carry out at 110 DEG C.The mass ratio of the quality of tosic acid and reaction-ure mixture (i.e. formula (b) compound and formula (c) compound) is 0.001:1 ~ 0.02:1; reaction times is 5 ~ 10 hours; with TLC monitoring reaction; treat 2-isobutyryl-1; 10-phenanthroline after completion of the reaction; removed under reduced pressure solvent; then be 1:1 ~ 1:9 by volume ratio; the ethyl acetate of preferred 1:4: the mixing solutions of sherwood oil is as leacheate; silica gel column chromatography obtains target product, i.e. formula (d) compound.Target product is through nuclear-magnetism and mass spectral characteristi.
In a preferred embodiment of the inventive method, the substituted aniline of formula (c) is by 1-5, preferred 1-4, and more preferably 1-3 identical or different is selected from C
1-C
6alkyl, C
1-C
6the aniline of the substituting group replacement of alkoxyl group, halogen and nitro.As an example, 2-aminotoluene can be mentioned, 3-monomethylaniline, 4-monomethylaniline, 23 dimethyl aniline, 2,4-xylidine, 2,5-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, 2，4，6-trimethyl aniline, bromo-2, the 6-xylidines of 4-, 2-ethylaniline, 2-ethyl-6-monomethylaniline, 2-isopropyl aniline, 2,6-Diethyl Aniline, 2,6-DIPA, 2-fluoroaniline, the fluoro-4-monomethylaniline of 2-, the fluoro-5-monomethylaniline of 2-, 2,4 difluorobenzene amine, 2,5-difluoroaniline, 2,6-difluoroaniline, 3,4-difluoroaniline, 2,3,4-trifluoromethyl aniline, 2,4,5-trifluoromethyl aniline, 2,4,6-trifluoromethyl aniline, 2,3,4,5,6-penta fluoro benzene amine, 3-chloroaniline, 2,6-DCA, 2，3，4-trichloroaniline, 245 trichloroaniline, 2,4,6-trichloroaniline, 2-bromaniline, the bromo-4-monomethylaniline of 2-, the bromo-4-fluoroaniline of 2-, the bromo-2-fluoroaniline of 4-, 2,6-dibromo aniline, the bromo-4-monomethylaniline of 2,6-bis-, the bromo-4-chloroaniline of 2,6-bis-, 2,4,6-bromamide, the chloro-4-fluoroaniline of the bromo-6-of 2-, the chloro-6-fluoroaniline of the bromo-4-of 2-, bromo-4, the 6-difluoroanilines of 2-, 3-N-methyl-p-nitroaniline, 4-anisidine, 2-methyl-4-anisidine and 4-phenetidine, most preferably 2,6-Diethyl Anilines.
C. chlorination 2-isobutyryl-1,10-phenanthroline contracting amine closes the synthesis of iron (II) title complex: formula (d) compound and iron protochloride are reacted, and obtains formula (I) compound
Wherein R
1-R
5as mutual-through type (I) define.
At rare gas element as under the protections such as nitrogen; iron protochloride is dissolved in not moisture with in the organic solvent of oxygen; form the solution of 0.001 ~ 0.1g/ml; operable organic solvent is selected from toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene, methylene dichloride or its mixture etc. for this reason, preferred tetrahydrofuran (THF).In order to obtain aforementioned solution of ferrous chloride, replacing iron protochloride itself, also can use chloride hydrate ferrous iron (FeCl
24H
2o).Separately by 2-isobutyryl-1; 10-phenanthroline contracting amine ligand (d) is dissolved in not moisture with in the organic solvent of oxygen; form the solution of 0.01 ~ 0.1g/ml; toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene, methylene dichloride or its mixture etc. are selected from equally to this operable organic solvent, preferred tetrahydrofuran (THF).Then at rare gas element as under the protection such as nitrogen, merge above-mentioned two solution (such as at room temperature merging), and under rare gas element is as protections such as nitrogen stirred at ambient temperature certain hour, such as room temperature for overnight.With TLC monitoring reaction, after question response is complete, by conventional post-treating methods such as suction filtration, washing and dryings, aftertreatment is carried out to reaction product, obtain formula (I) compound title complex.Described washing can with an organic solvent as anhydrous diethyl ether carries out.Title complex is characterized by ultimate analysis and infrared spectra.In this synthesis step, 2-isobutyryl-1,10-phenanthroline ligand (d) is 1:1-1.2:1 with the mol ratio of iron protochloride, is preferably 1.05:1-1.1:1.
In the above-mentioned methods, the mol ratio of the aluminium in described promotor and the iron in described Primary Catalysts is 30 ~ 900.In a specific embodiment, the mol ratio of the iron in the aluminium in described promotor and described Primary Catalysts is 100 ~ 700, is more preferably 148 ~ 196.Even if in the lower molar ratio range provided, the ethylene oligomerization activity in described method is still higher.
In the above-mentioned methods, the described aluminum cocatalyst that contains is selected from aluminium alkoxide compound and alkylaluminium cpd, preferred alkyl aluminum compound.The general formula of described alkylaluminium cpd is AlR
nx
m, wherein R is straight or branched C
1-C
8alkyl; X is halogen, preferred chlorine or bromine; N is the integer of 1 ~ 3, and m is the integer of 0 ~ 2, and m+n equals 3.Preferably, described alkylaluminium cpd is excellent in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride, more preferably triethyl aluminum.Described aikyiaiurnirsoxan beta is C
1-C
4alkylaluminoxane, wherein C
1-C
4alkyl is the alkyl of straight or branched; Preferably, described aikyiaiurnirsoxan beta is selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane or isobutyl aluminium alkoxide; Be more preferably methylaluminoxane.
In the above-mentioned methods, the reaction pressure 0.1 ~ 30MPa of described oligomerisation reaction, preferably 1 ~ 5MPa; Temperature of reaction is-20 ~ 150 DEG C, 30 ~ 100 minutes reaction times.In a specific embodiment, the temperature of described oligomerisation reaction is 0 ~ 80 DEG C.In another embodiment, the temperature of described oligomerisation reaction is 5 ~ 35 DEG C.In the described temperature range provided, not only there is higher ethylene oligomerization active, and reaction conditions is gentle, is conducive to industrial production.
In the above-mentioned methods, described Primary Catalysts mixes in ethene environment with promotor, is conducive to avoiding Primary Catalysts to contact separately with the direct of promotor, can be conducive to the katalysis giving full play to catalyzer.
The oligomerisation reaction condition that above-mentioned oligomerization relates to is known to those skilled in the art, and ethylene oligomerization method specifically comprises the steps:, and (1) carries out the operation such as hyperthermia drying, vacuum displacement to reaction system, guarantees anhydrous and oxygen-free in system; (2) use ethene to replace reaction system, make reaction system be in ethene environment; (3) in system, add water and solvent, fully stir; (4) in solvent, add promotor and pass into ethene displacement; (5) add Primary Catalysts again, pass into ethene and start oligomerisation reaction; (6) keep reaction pressure be 0.1 ~ 30MPa and temperature of reaction be at-20 ~ 150 DEG C reaction 30 ~ 100 minutes; (7) be cooled to-10 ~ 10 DEG C after stopped reaction, get reaction product gas-chromatography and carry out (GC) analysis.
By above-mentioned oligomerization, the ethylene oligomerization product of acquisition comprises C
4, C
6, C
8, C
10, C
12, C
14, C
16, C
18, C
20, C
22deng; The selectivity of alpha-olefin can reach more than 88%.After ethylene oligomerization terminates, take out a small amount of reaction mixture with in the dilute hydrochloric acid of 5% and after carry out GC analysis.Result shows, oligomerization activity can reach 10
7gmol
-1h
-1above.In addition, the remaining reaction mixture ethanolic soln of the dilute hydrochloric acid acidifying of 5% neutralizes, and does not obtain polymkeric substance.
Carry out ethylene oligomerization according to method provided by the invention, although containing water in reaction system, there is higher oligomerisation reaction on the contrary active during ethylene oligomerization, overcome technology prejudice.Even under the condition of low-down aluminium/iron ratio, also there is good oligomerisation reaction active, and the selectivity of alpha-olefin is high.According to the method in the present invention, abandon the aromatic solvent that toxicity is large, adopt ɑ-alkene to make solvent, without the aromatic series being difficult to be separated in product, not only eliminate pollution on the environment, simplify production technique, reduce production cost, improve the safety coefficient of production.Make solvent according to a certain ɑ-alkene corresponding with product, without the aromatic series being difficult to be separated in product, can use by direct effect comonomer.
Relative to prior art, instant invention overcomes technology prejudice, optimize oligomerisation reaction technique, not only oligomerization activity is high, and making ethylene oligomerization reaction process cause rapid, stable, low toxic and environment-friendly, catalytic effect and cost are balanced preferably, practical.Ethylene oligomerization reaction cost is declined to a great extent, and consider catalytic effect and production cost, industrial prospect is wide.
Embodiment
Below be only preferred embodiment of the present invention, scope of the present invention can not be limited with this.Namely every change of doing according to the present patent application the scope of the claims and modification, all should still remain within the scope of the patent.
embodiment 1
1. catalyzer chlorination 2-isobutyryl-1,10-phenanthroline contracting 2,6-Diethyl Aniline closes the synthesis of iron (II) title complex
A.2-the synthesis (see following reaction process) of isobutyryl-1,10-phenanthroline
In 250ml there-necked flask, drop into 1,10-phenanthroline 5.1g (28.3mmol), dissolve with 100ml toluene under nitrogen protection and magnetic agitation.At-60 DEG C, under agitation in there-necked flask, slowly drip 15ml triethyl aluminum (d=0.75g/ml, 56.6mmol), within about 15 minutes, dropwise, continue at such a temperature to stir 18h, be warming up to about 30 DEG C afterwards, continue to stir 10h.Then reaction mixture is cooled to about-30 DEG C, slowly adds 50ml distilled water wherein, then be warming up to 30 DEG C of stirring 10h.Then separatory, takes out organic phase, and inorganic phase dichloromethane extraction three times, the consumption of each methylene dichloride is 20ml, merges each organic phase.Removed under reduced pressure solvent.Afterwards, add 50ml oil of mirbane (1.205g/ml), and in 210 DEG C of backflow 18 hours.Filter, oil of mirbane is removed in underpressure distillation, obtains dark thick shape liquid substance.Be leacheate with the mixing solutions of ethyl acetate: sherwood oil=1:2 (volume ratio), silica gel column chromatography carried out to gained dark thick shape liquid substance, obtains brown product, heavy 2.1g, productive rate 30%.This product is defined as compound described in title a. through nuclear-magnetism and mass spectroscopy, i.e. 2-isobutyryl-1,10-phenanthroline.
Mass spectrum MS-EI:250.
Nmr analysis: 1H NMR (400MHz, CDCl3): δ 9.26 (dd, J=1.72,1H); 8.33 (s, 2H); 8.27 (dd, J=1.68,1H) 7.86 (d, J=8.8,1H); 7.80 (d, J=8.8,1H); 7.68 (dd, J=5.28,1H); 3.47 (m, J=7.24,1H); 1.10 (d, J=7.4,6H).
B. the synthesis (see following reaction process) of part 2-isobutyryl-1,10-phenanthroline contracting 2,6-Diethyl Aniline
In 100ml two mouthfuls of flasks that water trap is housed; drop into the 2-isobutyryl-1 obtained in 0.53g (2.12mmol) step a; 10-phenanthroline and 0.95g (6.36mmol) 2,6-Diethyl Aniline (mol ratio is 1:3) and 35ml is not moisture and the toluene of oxygen.Water trap is equipped with prolong, adds tosic acid 0.1g and reflux at 110 DEG C, react 6 hours.Removed under reduced pressure solvent, by ethyl acetate: the mixing solutions of sherwood oil=1:4 (volume ratio) is as leacheate, and silica gel column chromatography obtains glassy yellow product, heavy 0.65g, productive rate is 81%.This product confirms as compound described in title b. through nuclear-magnetism, mass spectrum and ultimate analysis, i.e. 2-isobutyryl-1,10-phenanthroline contracting 2,6-Diethyl Aniline.
Mass spectrum MS-EI:381.
Nmr analysis: 1H NMR (400MHz, CDCl3): δ 9.25 (dd, J=2.96,1H); 8.66 (d, J=8.36,1H); 8.33 (d, J=8.36,1H); 8.28 (dd, J=7.84,1H); 7.85 (dd, J=9.02,2H); 7.65 (dd, J=4.36,1H); 7.15 (d, J=7.52,2H); 7.06 (t, J=7.04,1H); 3.01 (m, J=7.84 ,-CNCH(CH3) 2,1H); 2.40 (m, J=7.52, phCH2CH3,4H); 1.58 (d, J=7.44 ,-CNCH(CH3) 2,6H); 1.20 (t, J=7.30, phCH2CH3,6H).
Ultimate analysis: C
26h
27n
3(381.51), theoretical value: C, 81.85; H, 7.13; N, 11.01.Observed value: C, 81.36; H, 7.23; N, 10.55.
C. chlorination 2-isobutyryl-1,10-phenanthroline contracting 2,6-Diethyl Aniline closes the synthesis (see following reaction process) of iron (II)
Under nitrogen protection, dissolve not moisture for 0.16g (1.25mmol) iron protochloride 20ml with the tetrahydrofuran (THF) of oxygen in two mouthfuls of flasks.Separately 2-isobutyryl-1, the 10-phenanthroline obtained in 0.52g (1.36mmol) step b contracting 2,6-Diethyl Aniline is dissolved in 20ml not moisture with in the tetrahydrofuran (THF) of oxygen.Then above-mentioned two solution are merged under at room temperature nitrogen protection.Reaction is carried out at once, and solution presents grey black.At room temperature, nitrogen protection is stirred and is spent the night.Use TLC monitoring, until 2-isobutyryl-1,10-phenanthroline contracting 2,6-diethylbenzene amine ligand disappears substantially.Suction filtration, washs with anhydrous diethyl ether.Vacuum-drying obtains silver gray solid.This solid is defined as compound described in title c., and namely chlorination 2-isobutyryl-1,10-phenanthroline contracting 2,6-Diethyl Aniline closes iron (II), and its results of elemental analyses is as follows.
Ultimate analysis: C
26h
27cl
2feN
3(508.26), theoretical value: C, 61.44; H, 5.35; N, 8.27. observed value: C, 61.79; H, 5.60; N, 8.13.
2. ethylene oligomerization reaction, specifically comprises the steps: that (1) carries out the operation such as hyperthermia drying, vacuum displacement to 300ml stainless steel cauldron, guarantees anhydrous and oxygen-free in system; (2) use ethene to replace reactor, make system be in ethene environment; (3) add water and solvent 1-hexene in a kettle., fully stir; (4) 1.37ml triethyl aluminum toluene solution (concentration is 715 μm of ol/ml) is added in a kettle .) and pass into ethene displacement; (5) 1 of the replacement of 2ml isobutyryl is added, 10-phenanthroline contracting amine closes the toluene solution of iron complex (2.5 μm of ol/ml), total amount of liquid is 100ml, with the weight of organic solvent 1-hexene for benchmark, the weight content of water is 5ppm, Al/Fe=196, passes into ethene and starts oligomerisation reaction; (6) ethylene pressure is kept to be 1MPa and temperature of reaction is react 30min at 30 DEG C; (7) stopped reaction, takes out a small amount of reaction product gas-chromatography and carries out (GC) analysis: oligomerization activity is 0.57 × 10
7gmol
-1(Fe) h
-1, oligomer content is respectively C
420.4%, C
6~ C
1045.29%, C
6~ C
1869.75% (wherein containing linear alpha-alkene 93.5%), C
20~ C
289.85%, K value 0.63.The remaining mixture ethanolic soln of the hcl acidifying of 5% neutralizes, and does not obtain polymkeric substance.Analytical results is in table one.
embodiment 2
Adopt the method for embodiment 1 to carry out ethylene oligomerization reaction, difference is, with the weight of solvent 1-hexene for Calculation Basis, the weight content of water is 20ppm, and analytical results is in table one.
embodiment 3
Adopt the method for embodiment 1 to carry out ethylene oligomerization reaction, difference is, with the weight of solvent 1-hexene for Calculation Basis, the weight content of water is 50ppm, and analytical results is in table one.
embodiment 4
Adopt the method for embodiment 1 to carry out ethylene oligomerization reaction, difference is, with the weight of solvent 1-octene for Calculation Basis, the weight content of water is 120ppm, and analytical results is in table one.
embodiment 5
Adopt the method for embodiment 1 to carry out ethylene oligomerization reaction, difference is, with the weight of solvent 1-octene for Calculation Basis, the weight content of water is 200ppm, and analytical results is in table one.
embodiment 6
Adopt the method for embodiment 1 to carry out ethylene oligomerization reaction, difference is, with the weight of solvent 1-octene for Calculation Basis, the weight content of water is 260ppm, and analytical results is in table one.
embodiment 7
Adopt the method for embodiment 1 to carry out ethylene oligomerization reaction, difference is, with the weight of solvent 1-octene for Calculation Basis, the weight content of water is 350ppm, and analytical results is in table one.
embodiment 8
Adopt the method for embodiment 1 to carry out ethylene oligomerization reaction, difference is, with the weight of solvent 1-hexene for Calculation Basis, the weight content of water is 200ppm, and temperature of reaction is 0 DEG C, and analytical results is in table one.
embodiment 9
Adopt the method for embodiment 1 to carry out ethylene oligomerization reaction, difference is, with the weight of solvent 1-hexene for Calculation Basis, the weight content of water is 200ppm, and temperature of reaction is-10 DEG C, and analytical results is in table one.
embodiment 10
Adopt the method for embodiment 1 to carry out ethylene oligomerization reaction, difference is, with the weight of solvent 1-hexene for Calculation Basis, the weight content of water is 200ppm, and temperature of reaction is-20 DEG C, and analytical results is in table one.
embodiment 11
Adopt the method for embodiment 1 to carry out ethylene oligomerization reaction, difference is, with the weight of solvent 1-hexene for Calculation Basis, the weight content of water is 200ppm, and temperature of reaction is 50 DEG C, and analytical results is in table one.
comparative example 1
(1) operation such as hyperthermia drying, vacuum displacement is carried out to 300ml stainless steel cauldron, guarantee anhydrous and oxygen-free in system; (2) use ethene to replace reactor, make system be in ethene environment; (3) add dry toluene 92ml in a kettle., fully stir; (4) 1.37ml triethyl aluminum toluene solution (concentration is 715 μm of ol/ml) is added in a kettle .) and pass into ethene displacement; (5), after adding the toluene solution of 1,10-phenanthroline contracting amine conjunction iron complex (concentration is 2.5 μm of ol/ml) that 2ml isobutyryl replaces in a solvent, make Al/Fe=196, pass into ethene and start oligomerisation reaction; (6) keep ethylene pressure be 1MPa and temperature of reaction be at 30 DEG C react 30 minutes; (7) stopped reaction, takes out a small amount of reaction product gas-chromatography and carries out (GC) analysis, the results are shown in Table 1.
As can be seen from Table 1, carry out ethylene oligomerization according to method provided by the invention, although containing water in system, there is higher oligomerisation reaction on the contrary active; Even under the condition of low-down aluminium/iron ratio, also there is good oligomerisation reaction active, and the selectivity of alpha-olefin is high; And according to the method in the present invention, abandoned the aromatic solvent that toxicity is large, and adopt alkene to make solvent, simultaneously active at guarantee oligomerisation reaction, improve the safety coefficient of reaction.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (10)
1. an ethylene oligomerization method; described ethene is comprising 1 of the replacement of the isobutyryl shown in following formula (I); 10-phenanthroline contracting amine closes iron (II) title complex to be Primary Catalysts, to carry out oligomerisation reaction containing in the reaction system of aluminum cocatalyst and solvent, and described solvent is C
nalpha-olefin, wherein 4 ﹤ n≤10,
In formula, R
1-R
5be selected from hydrogen, C independently of one another
1-C
6alkyl, halogen, C
1-C
6alkoxyl group and nitro.
2. method according to claim 1, is characterized in that, in described reaction system, with the weight of organic solvent for Calculation Basis, the weight content of described water is 5 ~ 350ppm, preferably 20 ~ 260ppm, most preferably is 50 ~ 200ppm.
3. method according to claim 1 and 2, is characterized in that, described solvent is selected from 1-hexene, 1-octene, 1-decene, 2-ethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 2,3-dimethyl-1-hexene, 2,4-dimethyl-1-hexene, 2,5-dimethyl-1-hexene, 3,4-dimethyl-1-hexene, 3,5-dimethyl-1-hexene, 4,5-dimethyl-1-hexene, 3,3-dimethyl-1-hexene, 4,4-dimethyl-1-hexene, 5,5-dimethyl-1-hexene, 2,3-diethyl-1-hexene, 2,4-diethyl-1-hexene, 3,4-diethyl-1-hexene, 3,3-diethyl-1-hexene, 4,4-diethyl-1-hexene, 2-ethyl-1-octene, 3-ethyl-1-octene, 4-ethyl-1-octene, 5-ethyl-1-octene, 6-ethyl-1-octene, 2,3-dimethyl-1-octene, 2,4-dimethyl-1-octene, 2,5-dimethyl-1-octene, 2,6-dimethyl-1-octene, 2,7-dimethyl-1-octene, 3,3-dimethyl-1-octene, 3,4-dimethyl-1-octene, 3,5-dimethyl-1-octene, 3,6-dimethyl-1-octene, 4,4-dimethyl-1-octene, 4,5-dimethyl-1-octene, 4,6-dimethyl-1-octene, 4,7-dimethyl-1-octene, 5,5-dimethyl-1-octene, 5,6-dimethyl-1-octene, 5,7-dimethyl-1-octene, 6,6-dimethyl-1-octene and 6,7-dimethyl-1-octene, be preferably selected from 1-hexene and 1-octene.
4. according to the method in claims 1 to 3 described in any one, it is characterized in that, in described reaction system, with the volume of organic solvent for Calculation Basis, the content of described Primary Catalysts is 2 ~ 500 μm of ol/L, preferably 20 ~ 100 μm of ol/L.
5. according to the method in Claims 1 to 4 described in any one, it is characterized in that, the mol ratio of the iron in the aluminium in described promotor and described Primary Catalysts is 30 ~ 900, preferably 100 ~ 700, be more preferably 148 ~ 196.
6. according to the method in Claims 1 to 5 described in any one, it is characterized in that, the R in described Primary Catalysts
1-R
5be selected from hydrogen, methyl, ethyl, n-propyl, sec.-propyl, fluorine, chlorine, bromine, methoxyl group, oxyethyl group and nitro independently of one another, preferred R
1and R
5for ethyl, and R
2-R
4be hydrogen.
7. according to the method in claim 1 ~ 6 described in any one, it is characterized in that, the described aluminum cocatalyst that contains is selected from aluminium alkoxide compound and alkylaluminium cpd, preferred alkyl aluminum compound.
8. according to the method in claim 1 ~ 7 described in any one, it is characterized in that, the general formula of described alkylaluminium cpd is AlR
nx
m, wherein R is straight or branched C
1-C
8alkyl; X is halogen, preferred chlorine or bromine; N is the integer of 1 ~ 3, and m is the integer of 0 ~ 2, and m+n equals 3; Preferably, described alkylaluminium cpd is excellent in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride, more preferably triethyl aluminum.
9. according to the method in claim 1 ~ 8 described in any one, it is characterized in that, the reaction pressure of described oligomerisation reaction is 0.1 ~ 30MPa, preferably 1 ~ 5MPa; Temperature of reaction is-20 ~ 150 DEG C, preferably 0 ~ 80 DEG C, most preferably 5 ~ 35 DEG C; Reaction times 30 ~ 100min.
10. according to the method in claim 1 ~ 9 described in any one, it is characterized in that, described Primary Catalysts mixes in ethene environment with promotor.
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